CN110845297A - Preparation method of 4,4 '-dibromo-9, 9' -spirobifluorene - Google Patents
Preparation method of 4,4 '-dibromo-9, 9' -spirobifluorene Download PDFInfo
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- BVIUGLKKCVUUJA-UHFFFAOYSA-N 4,4'-dibromo-9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C(C(=CC=C2)Br)=C2C21C1=CC=CC=C1C1=C2C=CC=C1Br BVIUGLKKCVUUJA-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 30
- DRKHIWKXLZCAKP-UHFFFAOYSA-N 1-bromo-2-(2-bromophenyl)benzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1Br DRKHIWKXLZCAKP-UHFFFAOYSA-N 0.000 claims abstract description 12
- RVFUJVKGAIBAQW-UHFFFAOYSA-N BrC1=C(C=CC=C1)C=1C(=CC=CC=1)C(=O)C1=C(C=CC=C1)C1=C(C=CC=C1)Br Chemical compound BrC1=C(C=CC=C1)C=1C(=CC=CC=1)C(=O)C1=C(C=CC=C1)C1=C(C=CC=C1)Br RVFUJVKGAIBAQW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013067 intermediate product Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000004321 preservation Methods 0.000 claims description 29
- -1 carbonate compound Chemical class 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- JMPVESVJOFYWTB-UHFFFAOYSA-N dipropan-2-yl carbonate Chemical compound CC(C)OC(=O)OC(C)C JMPVESVJOFYWTB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 9
- 238000007363 ring formation reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- UILJRKFLYXOSIR-UHFFFAOYSA-N BrC=1C=CC(C2=CC3=CC=CC=C3C12)=O Chemical compound BrC=1C=CC(C2=CC3=CC=CC=C3C12)=O UILJRKFLYXOSIR-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000006263 metalation reaction Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- WSFSSNUMVMOOMR-BJUDXGSMSA-N methanone Chemical compound O=[11CH2] WSFSSNUMVMOOMR-BJUDXGSMSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BQVRHBOGZLFYEZ-UHFFFAOYSA-N 2-(2-bromophenyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1Br BQVRHBOGZLFYEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/02—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/93—Spiro compounds
- C07C2603/94—Spiro compounds containing "free" spiro atoms
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 4,4' -dibromo-9, 9' -spirobifluorene, which takes 2,2' -dibromobiphenyl, n-butyllithium and carbonate compounds as raw materials to prepare an intermediate product bis (2' -bromo- [1,1' -biphenyl ] -2-yl) ketone: the intermediate product is dehydrated and subjected to ring closure reaction to obtain the 4,4 '-dibromo-9, 9' -spirobifluorene. The method has the advantages of simple synthesis process, easy purification of the product, good product purity, easy purchase of the used raw materials, low cost and higher yield, and is suitable for industrial production.
Description
Technical Field
The invention relates to a preparation method of 4,4 '-dibromo-9, 9' -spirobifluorene.
Background
In recent years, organic light-emitting devices (abbreviated as OLEDs) have been studied rapidly. Since the OLED has the advantages of active light emission, high response speed, low driving voltage, high brightness and flexibility, the OLED has wide application in the fields of illumination, instruments and instrument display. The spirofluorene compound has important application value in the field of organic electroluminescence. 4,4 '-dibromo-9, 9' -spirobifluorene is an important spirofluorene intermediate material, and the following two methods are mainly used for synthesizing 4,4 '-dibromo-9, 9' -spirobifluorene at present.
Firstly (Organic Letters, 2010, Vol.12, No.24, 5648-5651), 2 '-dibromobiphenyl is used as a raw material to react with n-butyllithium to obtain a metalation reagent, then the metalation reagent reacts with carbon dioxide to obtain 2' -bromo- [1,1 '-biphenyl ] -2-carboxylic acid, 4-bromofluorenone is obtained through dehydration ring closure reaction, 4-bromofluorenone reacts with the metalation reagent of 2,2' -dibromobiphenyl to obtain 4-bromo-9- (2 '-bromo- [1,1' -biphenyl ] -2-yl) -9H-fluorene-9-alcohol, and finally 4,4 '-dibromo-9, 9' -spirobifluorene is obtained through dehydration ring closure reaction; the synthetic route is shown as the following chart:
the disadvantages of this synthetic route are: (a) the reaction process involves heterogeneous reaction (gas-liquid reaction), and the operation is complex; (b) long synthetic route, multiple operation steps, low yield and high cost.
Method II (Organic Letters, 2009, Vol.11, No.12, 2607-2610), using 2,2' -dibromobiphenyl as raw material, reacting with n-butyl lithium to obtain metallation reagent, then reacting with 4-bromofluorenone to obtain 4-bromo-9- (2' -bromo- [1,1' -biphenyl)]-2-yl) -9H-fluorene-9-alcohol, and finally obtaining 4,4 '-dibromo-9, 9' -spirobifluorene through dehydration and ring closure reaction; the synthetic route is shown as the following chart:
；
the disadvantages of this synthetic route are: 4-bromofluorenone is expensive and not easy to obtain, and the cost of raw materials is high.
Both of the above two preparation methods relate to a key material, namely 4-bromofluorenone, and the research of documents shows that the 4-bromofluorenone preparation method is obtained by catalyzing C-C coupling by using a catalyst containing noble metal Pd and then performing ring closure reaction in most of other methods (CN 105237379A) except the method described in the synthesis method 1. The synthesis process of the 4-bromofluorenone is complex and expensive, so that the 4,4 '-dibromo-9, 9' -spirobifluorene is high in production cost and difficult to industrially produce, and the application of the 4-bromofluorenone is limited.
Disclosure of Invention
The invention aims to provide a preparation method of 4,4 '-dibromo-9, 9' -spirobifluorene, which has the advantages of low cost, easily purchased raw materials, short synthetic route, simple operation method, high yield and suitability for industrial production.
The invention takes 2,2' -dibromo biphenyl, n-butyl lithium and carbonate compounds as raw materials to prepare an intermediate product bis (2' -bromo- [1,1' -biphenyl ] -2-yl) ketone, and the intermediate product is subjected to dehydration and ring closure reaction to obtain 4,4' -dibromo-9, 9' -spirobifluorene. The structural formula of the 4,4 '-dibromo-9, 9' -spirobifluorene prepared by the invention is as follows:
the synthetic route is as follows:
the preparation method of the 4,4 '-dibromo-9, 9' -spirobifluorene provided by the invention comprises the following steps:
(1) preparing an intermediate product bis (2' -bromo- [1,1' -biphenyl ] -2-yl) methanone by using 2,2' -dibromo biphenyl, n-butyl lithium and a carbonate compound as raw materials:
(2) adding the intermediate product bis (2 '-bromo- [1,1' -biphenyl ] -2-yl) methanone into a solvent II, and reacting for 3-5 hours at 120-140 ℃ under the condition of heat preservation to obtain the 4,4 '-dibromo-9, 9' -spirobifluorene.
The specific operation of the step (1) is as follows: under the protection of inert gas, 2' -dibromobiphenyl and a solvent I are uniformly mixed, then n-butyllithium is dripped, a first heat preservation reaction is carried out after the dripping is finished, a carbonate compound is dripped after the first heat preservation reaction is finished, a second heat preservation reaction is carried out after the dripping is finished, water is added for quenching reaction after the second heat preservation reaction is finished, and then the intermediate product bis (2' -bromo- [1,1' -biphenyl ] -2-yl) ketone is obtained by filtering.
The molar ratio of the 2,2' -dibromobiphenyl to the n-butyllithium is 1.05-1.2: 1.0; the molar ratio of the 2,2' -dibromobiphenyl to the carbonate compound is 2.1-2.6: 1.0; the mass ratio of the bis (2 '-bromo- [1,1' -biphenyl ] -2-yl) ketone to the solvent II is 1.0: 6-9.
The temperature conditions of the dropwise adding of the n-butyl lithium and the primary heat preservation reaction are-85 ℃ to-95 ℃; the temperature conditions of the dropwise adding of the carbonate compound and the secondary heat preservation reaction are-65 ℃ to-75 ℃; the reaction was quenched by addition of water at room temperature.
The solvent I is any one of diethyl ether, tetrahydrofuran and methyl tert-butyl ether; the carbonate compound is any one of dimethyl carbonate, diethyl carbonate and diisopropyl carbonate; the inert gas is nitrogen or argon.
The solvent II is methanesulfonic acid or trifluoromethanesulfonic acid.
The dropping time of the n-butyllithium and the carbonate compound in the invention is generally 20-60 minutes.
The invention has the advantages that: the invention discloses a preparation method of 4,4 '-dibromo-9, 9' -spirobifluorene, which has the advantages of simple synthesis process, easy purification of products, good product purity, easy purchase of used raw materials, low cost, high yield and suitability for industrial production.
Drawings
FIG. 1 is a photograph of the product prepared in example 11A HNMR map;
FIG. 2 is a photograph of the product prepared in example 113A CNMR map.
Detailed Description
Example 1
The preparation method of the 4,4 '-dibromo-9, 9' -spirobifluorene comprises the following steps:
(1) installing N on a 2L three-mouth bottle2Side tube, thermometer, sleeve, liquid seal, mechanical stirring, constant pressure dropping funnel and drying tube. Adding 137.3g (0.44 mol) of 2,2' -dibromobiphenyl and 823.8g of tetrahydrofuran into a 2L three-necked bottle, carrying out nitrogen protection, mechanically stirring, placing in a low-temperature bath for cooling, dropwise adding 167.6mL (0.419 mol) of n-butyllithium (2.5M n-hexane solution) into the bottle at the temperature of-85 to-95 ℃, dropwise adding for 40 minutes, and carrying out heat preservation reaction for 1.5 to 2 hours at the temperature of-85 to-95 ℃ after dropwise adding (namely, carrying out primary heat preservation reaction); after the primary heat preservation reaction is finished, 18.0g (0.2 mol) of dimethyl carbonate is dripped into a bottle at the temperature of-65 to-75 ℃, the dripping time is 30 minutes, after the dripping is finished, the heat preservation reaction is continuously carried out for 2 to 3 hours at the temperature of-65 to-75 ℃ (namely, the secondary heat preservation reaction), the mixture is transferred to the room temperature after the secondary heat preservation reaction is finished and is continuously stirred, when the temperature of the system is raised to the room temperature, 180g of water is added into the reaction system for quenching reaction, the reaction system is stirred for 0.5 hour, the white-like solid is obtained by suction filtration, the white-like solid is recrystallized by using 1, 2-dichloroethane, the room temperature suction filtration is carried out, and the obtained white solid is bis (2' -bromo- [1,1]-2-yl) methanone, yield 68.3%, HPLC purity 98.5%;
(2) installing a thermometer and a sleeve on a 1L three-necked bottle, mechanically stirring a spherical condenser pipe, adding 103.4g (0.21 mol) of bis (2 '-bromo- [1,1' -biphenyl ] -2-yl) methanone and 827.2g of methanesulfonic acid into the 1L three-necked bottle, and carrying out heat preservation reaction at 120-130 ℃ for 4-5 hours. And after the heat preservation is finished, cooling the temperature of the system to 20-25 ℃, carrying out suction filtration, washing the filter cake for 2-3 times, recrystallizing the filter cake by using dimethylbenzene, and carrying out suction filtration at room temperature to obtain a white powdery solid 4,4 '-dibromo-9, 9' -spirobifluorene with the yield of 78.2% and the HPLC purity of 99.2%.
Example 2
The preparation method of the 4,4 '-dibromo-9, 9' -spirobifluorene comprises the following steps:
(1) installing N on a 2L three-mouth bottle2Side tube, thermometer, sleeve, liquid seal, mechanical stirring, constant pressure dropping funnel and drying tube. Adding into a 2L three-necked bottle143.5g (0.46 mol) of 2,2' -dibromobiphenyl and 861g of methyl tert-butyl ether, stirring mechanically under the protection of nitrogen, placing in a low-temperature bath to reduce the temperature, dripping 170.4mL (0.426 mol) of n-butyl lithium (2.5M n-hexane solution) into a bottle at the temperature of-85 to-95 ℃ for 30 minutes, and then carrying out heat preservation reaction at the temperature of-85 to-95 ℃ for 1.0 to 1.5 hours (namely primary heat preservation reaction). After the primary heat preservation reaction is finished, 18.0g (0.2 mol) of diethyl carbonate is dripped into the bottle at the temperature of between 65 ℃ below zero and 75 ℃ below zero for 20 minutes, and heat preservation is continuously carried out for 3 to 4 hours at the temperature of between 65 ℃ below zero and 75 ℃ below zero after the dripping is finished (namely, the secondary heat preservation reaction). After the secondary heat preservation reaction is finished, transferring the mixture to a three-necked flask to be stirred continuously at room temperature, adding 180g of water into the reaction system to quench and react when the temperature of the system is raised to the room temperature, stirring for 0.5 hour, performing suction filtration to obtain a white-like solid, recrystallizing the white-like solid by using 1, 2-dichloroethane, and performing suction filtration at the room temperature to obtain the white solid which is bis (2 '-bromo- [1,1' -biphenyl ] s]-2-yl) methanone, yield 68.6%, HPLC purity 98.4%.
(2) Installing a thermometer and a sleeve on a 1L three-necked bottle, mechanically stirring a spherical condenser pipe, adding 103.4g (0.21 mol) of bis (2 '-bromo- [1,1' -biphenyl ] -2-yl) methanone and 723.8g of trifluoromethanesulfonic acid into the 1L three-necked bottle, and reacting at 130-140 ℃ for 3-4 hours. And after the heat preservation is finished, cooling the temperature of the system to 20-25 ℃, carrying out suction filtration, washing the filter cake for 2-3 times, recrystallizing the filter cake by using dimethylbenzene, and carrying out suction filtration at room temperature to obtain a white powdery solid 4,4 '-dibromo-9, 9' -spirobifluorene with the yield of 78.3% and the HPLC purity of 99.3%.
Figure 1 is a 1h nmr plot of the product prepared in example 1, characterized as follows:
1H NMR (CDCl3, 500 MHz)，δ: 8.67 (d, 2H,J= 8.0 Hz)，7.52 (d, 2H,J= 8.0Hz)，7.43 (t, 2H,J= 7.5 Hz)，7.18 (t, 2H,J= 7.5 Hz)，6.95 (t, 2H,J= 8.0 Hz)，6.73 (d, 2H,J= 8.0 Hz)，6.66 (d, 2H,J= 7.5 Hz)。
fig. 2 is a 13CNMR picture of the product prepared in example 1, characterized as follows:
13CNMR (CDCl3, 125MHz)，δ: 151.15, 148.53, 140.92, 139.86, 132.88, 128.72,128.61, 127.71, 123.88, 123.64, 122.98, 116.78, 65.80。
as can be seen from the analysis of fig. 1 and 2, the product of example 1 is identified as 4,4 '-dibromo-9, 9' -spirobifluorene, and its structural formula is as follows:
Claims (6)
1. a method for preparing 4,4 '-dibromo-9, 9' -spirobifluorene, which is characterized by comprising the following steps:
(1) preparing an intermediate product bis (2' -bromo- [1,1' -biphenyl ] -2-yl) methanone by using 2,2' -dibromo biphenyl, n-butyl lithium and a carbonate compound as raw materials:
(2) adding the intermediate product bis (2 '-bromo- [1,1' -biphenyl ] -2-yl) methanone into a solvent II, and reacting for 3-5 hours at 120-140 ℃ under the condition of heat preservation to obtain the 4,4 '-dibromo-9, 9' -spirobifluorene.
2. The method for producing 4,4 '-dibromo-9, 9' -spirobifluorene according to claim 1, wherein: the specific operation of the step (1) is as follows: under the protection of inert gas, 2' -dibromobiphenyl and a solvent I are uniformly mixed, then n-butyllithium is dripped, a first heat preservation reaction is carried out after the dripping is finished, a carbonate compound is dripped after the first heat preservation reaction is finished, a second heat preservation reaction is carried out after the dripping is finished, water is added for quenching reaction after the second heat preservation reaction is finished, and then the intermediate product bis (2' -bromo- [1,1' -biphenyl ] -2-yl) ketone is obtained by filtering.
3. The method for producing 4,4 '-dibromo-9, 9' -spirobifluorene according to claim 1 or 2, characterized in that: the molar ratio of the 2,2' -dibromobiphenyl to the n-butyllithium is 1.05-1.2: 1.0; the molar ratio of the 2,2' -dibromobiphenyl to the carbonate compound is 2.1-2.6: 1.0; the mass ratio of the bis (2 '-bromo- [1,1' -biphenyl ] -2-yl) ketone to the solvent II is 1.0: 6-9.
4. The method for producing 4,4 '-dibromo-9, 9' -spirobifluorene according to claim 2, wherein: the temperature conditions of the dropwise adding of the n-butyl lithium and the primary heat preservation reaction are-85 ℃ to-95 ℃; the temperature conditions of the dropwise adding of the carbonate compound and the secondary heat preservation reaction are-65 ℃ to-75 ℃; the reaction was quenched by addition of water at room temperature.
5. The method for producing 4,4 '-dibromo-9, 9' -spirobifluorene according to claim 2, wherein: the solvent I is any one of diethyl ether, tetrahydrofuran and methyl tert-butyl ether; the carbonate compound is any one of dimethyl carbonate, diethyl carbonate or diisopropyl carbonate; the inert gas is nitrogen or argon.
6. The method for producing 4,4 '-dibromo-9, 9' -spirobifluorene according to claim 1 or 2, characterized in that: the solvent II is methanesulfonic acid or trifluoromethanesulfonic acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942444A (en) * | 2012-11-09 | 2013-02-27 | 烟台海川化学制品有限公司 | Synthesis method of 2,2'-dibromo-9,9'-spirobifluorene |
Non-Patent Citations (1)
| Title |
|---|
| CONG FAN等: ""Tri-, Tetra- and Pentamers of9,9`-Spirobifluorenes through Full ortho-Linkage: High Triplet-Energy Pure", 《ORGANIC LETTERS》 * |
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